CA2573765C - Use of phosphated alcanols as dispersants, emulsifiers, hydrotropes, wetting agents and compatibility agents in agricultural compositions - Google Patents
Use of phosphated alcanols as dispersants, emulsifiers, hydrotropes, wetting agents and compatibility agents in agricultural compositions Download PDFInfo
- Publication number
- CA2573765C CA2573765C CA2573765A CA2573765A CA2573765C CA 2573765 C CA2573765 C CA 2573765C CA 2573765 A CA2573765 A CA 2573765A CA 2573765 A CA2573765 A CA 2573765A CA 2573765 C CA2573765 C CA 2573765C
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- CA
- Canada
- Prior art keywords
- phosphated
- propylheptanol
- formulation
- alkoxylate
- adjuvant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/362—Phosphates or phosphites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/34—Derivatives of acids of phosphorus
- C11D1/345—Phosphates or phosphites
Abstract
The present invention relates to the use of phosphated 2-propylheptanol, phosphated 2-proyplheptanol alkoxylate and/or mixtures thereof in agricultural formulations. The invention also relates to agricultural formulations comprising the aforementioned adjuvants, and to methods of treating a plant with the agricultural formulations of the invention.
Description
USE OF PHOSPHATED ALCANOLS AS DISPERSANTS, EMULSIFIERS, HYDROTROPES, WETTING AGENTS AND COMPATIBILITY AGENTS IN
AGRICULTURAL COMPOSITIONS
The present invention relates to the use of phosphated 2-propylheptanol or a phosphated 2-propylheptanol alkoxylate as an adjuvant in agricultural formulations. More specifically, it relates to the use of phosphated hydroxyl compounds as a dispersant, emulsifier, hydrotrope, wetting agent, compatability agent and the like in agricultural formulations.
Background of the Invention The agricultural chemical formulator has the difficult task of creating a product that balances bioefficacy, toxicity, cost, shelf life and user friendliness.
Of particular importance to the activity of an agricultural formulation is the ability of an aqueous solution to spread evenly over a surface, the so-called wetting ability, and the effective uptake of the active ingredient by the plant to be treated. For example, in agricultural formulations, efficacy benefits from a good wetting of the plant surface and uptake of the active ingredient.
Adjuvants are added to agricultural formulations to improve activity, thereby reducing the amounts of active ingredients necessary, resulting in lower application cost. They generally take the form of surface-active or salt like compounds and depending on their mode of action, they are classified as modifiers, activators, fertilizers and/or pH buffers.
Surfactants are generally regarded as modifiers and/or activators as they improve wetting properties and uptake of the active ingredients in the agricultural formulation. Additionally, some surfactants improve the solubility of active ingredients in formulations thereby eliminating serious issues such as product separation and/or crystallization.
Anionic, cationic, amphoteric and nonionic surfactants are all known and used in agricultural applications depending on the desired effect. For
AGRICULTURAL COMPOSITIONS
The present invention relates to the use of phosphated 2-propylheptanol or a phosphated 2-propylheptanol alkoxylate as an adjuvant in agricultural formulations. More specifically, it relates to the use of phosphated hydroxyl compounds as a dispersant, emulsifier, hydrotrope, wetting agent, compatability agent and the like in agricultural formulations.
Background of the Invention The agricultural chemical formulator has the difficult task of creating a product that balances bioefficacy, toxicity, cost, shelf life and user friendliness.
Of particular importance to the activity of an agricultural formulation is the ability of an aqueous solution to spread evenly over a surface, the so-called wetting ability, and the effective uptake of the active ingredient by the plant to be treated. For example, in agricultural formulations, efficacy benefits from a good wetting of the plant surface and uptake of the active ingredient.
Adjuvants are added to agricultural formulations to improve activity, thereby reducing the amounts of active ingredients necessary, resulting in lower application cost. They generally take the form of surface-active or salt like compounds and depending on their mode of action, they are classified as modifiers, activators, fertilizers and/or pH buffers.
Surfactants are generally regarded as modifiers and/or activators as they improve wetting properties and uptake of the active ingredients in the agricultural formulation. Additionally, some surfactants improve the solubility of active ingredients in formulations thereby eliminating serious issues such as product separation and/or crystallization.
Anionic, cationic, amphoteric and nonionic surfactants are all known and used in agricultural applications depending on the desired effect. For
2 example, nonionic surfactants are known to be good wetting agents, and are often present in agricultural formulations. Many nonionic surfactants are not soluble enough in solutions with a high amount of electrolytes, such as alkali and/or alkaline complexing agents, salts, and the like and therefore need the presence of a hydrotrope to improve the solubility. A number of hydrotropes for nonionic surfactants have been described in various publications. Examples of such hydrotropes are ethanol, sodium xylene sulphonate, sodium cumene sulphonate, alkyl glycosides, and phosphated alkoxylated alcohols.
However, there is still a need for new efficient surfactants that can improve activity, act as effective hydrotropes, and are compatible for the achievement of stable formulations delivering optimal performance. The objective of the present invention is, therefore, to find a new adjuvant, especially a hydrotrope that is efficient in formulating agricultural compositions, which compositions will remain homogeneous upon dilution, and where the performance of the compositions is good.
Accordingly, it is an object of the present invention to provide an improved agricultural adjuvant. It is also an object of the invention to provide a stable, agricultural formulation having improved activity. These and other objects are achieved by the adjuvants/formulations of the present invention.
Summary of the Invention The present invention relates to the use of phosphated 2-propylheptanol, phosphated 2-propylheptanol alkoxylate and/or mixtures thereof as agricultural adjuvants. The invention also relates to agricultural formulations comprising same, and to methods of treating a plant with the agricultural formulations of the invention.
Detailed Description of the Invention The invention relates to the use of phosphated 2-propylheptanol or phosphated 2-propylheptanol alkoxylates as an adjuvant, for example a hydrotrope, in agricultural formulations. More specifically, it relates to an agricultural adjuvant that comprises at least one phosphated hydroxyl compound. The adjuvant of the invention can effectively be utilized as a dispersant, emulsifier, hydrotrope, wetting agent, compatability agent and /or the like in agricultural formulations. In this regard, it has been found that phosphated 2-propylheptanol or a phosphated 2-
However, there is still a need for new efficient surfactants that can improve activity, act as effective hydrotropes, and are compatible for the achievement of stable formulations delivering optimal performance. The objective of the present invention is, therefore, to find a new adjuvant, especially a hydrotrope that is efficient in formulating agricultural compositions, which compositions will remain homogeneous upon dilution, and where the performance of the compositions is good.
Accordingly, it is an object of the present invention to provide an improved agricultural adjuvant. It is also an object of the invention to provide a stable, agricultural formulation having improved activity. These and other objects are achieved by the adjuvants/formulations of the present invention.
Summary of the Invention The present invention relates to the use of phosphated 2-propylheptanol, phosphated 2-propylheptanol alkoxylate and/or mixtures thereof as agricultural adjuvants. The invention also relates to agricultural formulations comprising same, and to methods of treating a plant with the agricultural formulations of the invention.
Detailed Description of the Invention The invention relates to the use of phosphated 2-propylheptanol or phosphated 2-propylheptanol alkoxylates as an adjuvant, for example a hydrotrope, in agricultural formulations. More specifically, it relates to an agricultural adjuvant that comprises at least one phosphated hydroxyl compound. The adjuvant of the invention can effectively be utilized as a dispersant, emulsifier, hydrotrope, wetting agent, compatability agent and /or the like in agricultural formulations. In this regard, it has been found that phosphated 2-propylheptanol or a phosphated 2-
3 propylheptanol alkoxylate where the alkoxylate on the average comprises 1-20, preferably 1-15, more preferably 2-10, and most preferably 2-6 ethyleneoxy units and 0-3, preferably 0-2 propyleneoxy and/or butyleneoxy units, is an efficient hydrotrope and activity improver in agricultural formulations. The adjuvants of the invention improve wetting and uptake of active ingredients by a plant, resulting in a higher activity at a given application rate.
In another embodiment, the invention relates to aqueous agricultural formulations comprising at least one agricultural active, and 0.1-30, preferably 0.1-20, and most preferably 0.1-10% by weight of the adjuvant of the present invention.
The adjuvants of the invention can be used with any active ingredient in order to improve efficacy by improving the dispersion or emulsions properties in the application tank, or modifying the spreading and/or penetration properties of the spray solution on the plant. Examples of active ingredients include, but are not limited to herbicides, fungicides, insecticides, plant growth regulators and the like.
The following is a non-limiting list of active ingredients that can be employed:
Herbicides (examples, but not limited to):
= amide herbicides allidochlor beflubutamid benzadox benzipram bromobutide cafenstrole CDEA
cvprazole
In another embodiment, the invention relates to aqueous agricultural formulations comprising at least one agricultural active, and 0.1-30, preferably 0.1-20, and most preferably 0.1-10% by weight of the adjuvant of the present invention.
The adjuvants of the invention can be used with any active ingredient in order to improve efficacy by improving the dispersion or emulsions properties in the application tank, or modifying the spreading and/or penetration properties of the spray solution on the plant. Examples of active ingredients include, but are not limited to herbicides, fungicides, insecticides, plant growth regulators and the like.
The following is a non-limiting list of active ingredients that can be employed:
Herbicides (examples, but not limited to):
= amide herbicides allidochlor beflubutamid benzadox benzipram bromobutide cafenstrole CDEA
cvprazole
4 dimethenamid dimethenamid-P
diphenamid epronaz etnipromid fentrazamide flupoxam fomesafen halosafen isocarbamid isoxaben napropamide naptalam pethoxamid propyzamide guinonamid tebutam o anilide herbicides chioranocryl cisanilide clomeprop cypromid diflufenican etobenzanid fenasulam flufenacet flufenican mefenacet mefluidide metamifop monalide naproanilide pentanochlor picolinafen propanil = arylalanine herbicides benzoylprop flamprop flamprop-M
= chloroacetanilide herbicides acetochior alachlor butachlor butenachior delachlor diethatyl dimethachlor metozachlor metolachlor
diphenamid epronaz etnipromid fentrazamide flupoxam fomesafen halosafen isocarbamid isoxaben napropamide naptalam pethoxamid propyzamide guinonamid tebutam o anilide herbicides chioranocryl cisanilide clomeprop cypromid diflufenican etobenzanid fenasulam flufenacet flufenican mefenacet mefluidide metamifop monalide naproanilide pentanochlor picolinafen propanil = arylalanine herbicides benzoylprop flamprop flamprop-M
= chloroacetanilide herbicides acetochior alachlor butachlor butenachior delachlor diethatyl dimethachlor metozachlor metolachlor
5 S-metolachlor pretilachior propachior propisochlor prynachlor terbuchlor thenylchlor xylachlor = sulfonanilide herbicides benzofluor cloransulam diclosulam florasulam flumetsulam metosulam perfluidone pyrimisulfan profluazol = sulfonamide herbicides asulam carbasulam fenasulam oryzalin penoxsulam o thioamide herbicides bencarbazone chlorthiamid = antibiotic herbicides bilanafos = aromatic acid herbicides o benzoic acid herbicides chioramben dicamba 2,3,6-TBA
tricamba
tricamba
6 = pyrimidinyloxybenzoic acid herbicides bispyribac pyriminobac = pyrimidinylthiobenzoic acid herbicides pyrithiobac o phthalic acid herbicides chlorthal o picolinic acid herbicides aminopyralid clopyralid picloram o quinolinecarboxylic acid herbicides guinclorac guinmerac = arsenical herbicides cacodylic acid CMA
DSMA
hexaflurate MAA
MAMA
MSMA
potassium arsenite sodium arsenite = benzoylcyclohexanedione herbicides mesotrione sulcotrione = benzofuranyl alkylsulfonate herbicides benfuresate ethofumesate = carbamate herbicides asulam carboxazole chiorprocarb dichlormate fenasulam karbutilate terbucarb = carbanilate herbicides barban BCPC
DSMA
hexaflurate MAA
MAMA
MSMA
potassium arsenite sodium arsenite = benzoylcyclohexanedione herbicides mesotrione sulcotrione = benzofuranyl alkylsulfonate herbicides benfuresate ethofumesate = carbamate herbicides asulam carboxazole chiorprocarb dichlormate fenasulam karbutilate terbucarb = carbanilate herbicides barban BCPC
7 carbasulam carbetamide CEPC
chlorbufam chlorpropham CPPC
desmedipham phenisopham phenmedipham phenmedipham-ethyl propham swep = cyclohexene oxime herbicides alloxydim butroxydim clethodim cloproxydim cycloxydim profoxydim sethoxydim tepraloxydim tralkoxydim = cyclopropylisoxazole herbicides isoxachlortole isoxaflutole = dicarboximide herbicides benzfendizone cinidon-ethyl flumezin flumiclorac flumioxazin flumipropyn = dinitroaniline herbicides benfluralin butralin dinitramine ethalfluralin fluchloralin isopropalin methalpropalin nitralin oryzalin pendimethalin prodiamine
chlorbufam chlorpropham CPPC
desmedipham phenisopham phenmedipham phenmedipham-ethyl propham swep = cyclohexene oxime herbicides alloxydim butroxydim clethodim cloproxydim cycloxydim profoxydim sethoxydim tepraloxydim tralkoxydim = cyclopropylisoxazole herbicides isoxachlortole isoxaflutole = dicarboximide herbicides benzfendizone cinidon-ethyl flumezin flumiclorac flumioxazin flumipropyn = dinitroaniline herbicides benfluralin butralin dinitramine ethalfluralin fluchloralin isopropalin methalpropalin nitralin oryzalin pendimethalin prodiamine
8 profluralin trifluralin = dinitrophenol herbicides dinofenate dinoprop dinosam dinoseb dinoterb DNOC
etinofen medinoterb = diphenyl ether herbicides ethox en o nitrophenyl ether herbicides acifluorfen aclonifen bifenox chlomethoxvfen chlornitrofen etnipromid fluorodifen fluoroglycofen fluoronitrofen fomesafen fur loxyfen halosafen lactofen nitrofen nitrofluorfen oxyfluorfen = dithiocarbamate herbicides dazomet metam = halogenated aliphatic herbicides alorac chloropon dalapon flupropanate hexachloroacetone iodomethane methyl bromide monochloroacetic acid SMA
TCA
etinofen medinoterb = diphenyl ether herbicides ethox en o nitrophenyl ether herbicides acifluorfen aclonifen bifenox chlomethoxvfen chlornitrofen etnipromid fluorodifen fluoroglycofen fluoronitrofen fomesafen fur loxyfen halosafen lactofen nitrofen nitrofluorfen oxyfluorfen = dithiocarbamate herbicides dazomet metam = halogenated aliphatic herbicides alorac chloropon dalapon flupropanate hexachloroacetone iodomethane methyl bromide monochloroacetic acid SMA
TCA
9 = imidazolinone herbicides imazamethabenz imazamox imazapic imazapyr imazaguin imazethapyr = inorganic herbicides ammonium sulfamate borax calcium chlorate copper sulfate ferrous sulfate potassium azide potassium cyanate sodium azide sodium chlorate sulfuric acid = nitrile herbicides bromobonil bromoxynil chloroxynil dichiobenil iodobonil ioxynil pyraclonil = organophosphorus herbicides amiprofos-methyl anilofos bensulide bilanafos butamifos 2,4-DEP
DMPA
EBEP
fosamine glufosinate glyphosate piperophos = phenoxy herbicides bromofenoxim clomeprop 2,4-DEB
2,4-DEP
difenopenten disul erbon etnipromid 5 fenteracol trifopsime o phenoxyacetic herbicides 2,4-D
DMPA
EBEP
fosamine glufosinate glyphosate piperophos = phenoxy herbicides bromofenoxim clomeprop 2,4-DEB
2,4-DEP
difenopenten disul erbon etnipromid 5 fenteracol trifopsime o phenoxyacetic herbicides 2,4-D
10 3,4-DA
MCPA
MCPA-thioethyl 2,4,5-T
o phenoxybutyric herbicides 2,4-DB
3,4-DB
MCPB
2,4,5-TB
o phenoxypropionic herbicides clo ro dichlorprop dichlorprop-P
3,4-DP
fenoprop mecoprop mecoprop-P
= aryloxyphenoxypropionic herbicides chlorazifop clodinafop clofop cyhalofop diclofop fenoxaprop fenoxaprop-P
fenthiaprop fluazifop fluazifop-P
haloxvfop haloxyfop-P
isoxapyrifop metamifop propaquizafop
MCPA
MCPA-thioethyl 2,4,5-T
o phenoxybutyric herbicides 2,4-DB
3,4-DB
MCPB
2,4,5-TB
o phenoxypropionic herbicides clo ro dichlorprop dichlorprop-P
3,4-DP
fenoprop mecoprop mecoprop-P
= aryloxyphenoxypropionic herbicides chlorazifop clodinafop clofop cyhalofop diclofop fenoxaprop fenoxaprop-P
fenthiaprop fluazifop fluazifop-P
haloxvfop haloxyfop-P
isoxapyrifop metamifop propaquizafop
11 quizalofop quizalofop-P
trifop = phenylenediamine herbicides dinitramine prodiamine = phenyl pyrazolyl ketone herbicides benzofenap pyrasulfotole pyrazolynate pyrazoxyfen topramezone = pyrazolylphenyl herbicides fluazolate pyraflufen = pyridazine herbicides credazine pyridafol pyridate = pyridazinone herbicides brompyrazon chloridazon dimidazon flufenpyr metflurazon norfiurazon oxapyrazon pydanon = pyridine herbicides aminopyralid cliodinate clopyralid dithiopyr fluroxypyr haloxydine picloram picolinafen riclor thiazopyr triclopyr
trifop = phenylenediamine herbicides dinitramine prodiamine = phenyl pyrazolyl ketone herbicides benzofenap pyrasulfotole pyrazolynate pyrazoxyfen topramezone = pyrazolylphenyl herbicides fluazolate pyraflufen = pyridazine herbicides credazine pyridafol pyridate = pyridazinone herbicides brompyrazon chloridazon dimidazon flufenpyr metflurazon norfiurazon oxapyrazon pydanon = pyridine herbicides aminopyralid cliodinate clopyralid dithiopyr fluroxypyr haloxydine picloram picolinafen riclor thiazopyr triclopyr
12 = pyrimidinediamine herbicides iprymidam tioclorim = quaternary ammonium herbicides cyperguat diethamguat difenzoguat diguat morfamguat paraguat = thiocarbamate herbicides butylate cycloate di-allate EPTC
esprocarb ethiolate isopolinate methiobencarb molinate orbencarb pebulate prosulfocarb pyributicarb sulfallate thiobencarb tiocarbazil tri-allate vernolate = thiocarbonate herbicides dimexano EXD
proxan = thiourea herbicides methiuron = triazine herbicides dipropetryn triaziflam trihydroxytriazine o chiorotriazine herbicides atrazine chiorazine cyanazine
esprocarb ethiolate isopolinate methiobencarb molinate orbencarb pebulate prosulfocarb pyributicarb sulfallate thiobencarb tiocarbazil tri-allate vernolate = thiocarbonate herbicides dimexano EXD
proxan = thiourea herbicides methiuron = triazine herbicides dipropetryn triaziflam trihydroxytriazine o chiorotriazine herbicides atrazine chiorazine cyanazine
13 cyprazine eglinazine ipazine mesoprazine procyazine proglinazine propazine sebuthylazine simazine terbuthylazine trietazine o methoxytriazine herbicides atraton methometon prometon secbumeton simeton terbumeton o methylthiotriazine herbicides ametryn aziprotryne cyanatryn desmetryn dimethametryn methoprotryne prometryn simetryn terbutryn = triazinone herbicides ametridione amibuzin hexazinone isomethiozin metamitron metribuzin = triazole herbicides amitrole cafenstrole epronaz flupoxam =. triazolone herbicides amicarbazone bencarbazone carfentrazone
14 flucarbazone propoxycarbazone sulfentrazone = triazolopyrimidine herbicides cloransulam diclosulam florasulam flumetsulam metosulam penoxsulam = uracil herbicides butafenacil bromacil flupropacil isocil lenacil terbacil = urea herbicides benzthiazuron cumyluron cycluron dichloralurea diflufenzopyr isonoruron isouron methabenzthiazuron monisouron noruron o . phenylurea herbicides anisuron buturon chlorbromuron chloreturon chlorotoluron chloroxuron dmmuron difenoxuron dimefuron diuron fenuron fluometuron fluothiuron isoproturon linuron methiuron methyldymron metobenzuron metobromuron 5 metoxuron monolinuron monuron neburon parafluron 10 phenobenzuron siduron tetrafluron thidiazuron o sulfonylurea herbicides
15 = pyrimidinylsulfonylurea herbicides amidosulfuron azimsulfuron bensulfuron chiorimuron cyclosulfamuron ethoxysulfuron flazasulfuron flucetosulfuron flupyrsulfuron foramsulfuron halosulfuron imazosulfuron mesosulfuron nicosulfuron orthosulfamuron oxasulfuron primisulfuron pyrazosulfuron rimsulfuron sulfometuron sulfosulfuron trifloxysulfuron = triazinylsulfonylurea herbicides chlorsulfuron cinosulfuron ethametsulfuron iodosulfuron metsulfuron prosulfuron thifensulfuron
16 triasulfuron tribenuron triflusulfuron tritosulfuron o thiadiazolylurea herbicides buthiuron ethidimuron tebuthiuron thiazafluron thidiazuron = unclassified herbicides acrolein allyl alcohol azafenidin benazolin bentazone benzobicyclon buthidazole calcium cyanamide cambendichlor chlorfenac chlorfenprop chlorflurazole chlorfiurenol cinmethylin clomazone CPMF
cresol ortho-dichlorobenzene dimepiperate endothal fiuoromidine fluridone flurochioridone flurtamone fluthiacet indanofan methazole methyl isothiocyanate nipyraclofen OCH
oxadiarpyl oxadiazon oxaziclomefone pentachlorophenol pentoxazone
cresol ortho-dichlorobenzene dimepiperate endothal fiuoromidine fluridone flurochioridone flurtamone fluthiacet indanofan methazole methyl isothiocyanate nipyraclofen OCH
oxadiarpyl oxadiazon oxaziclomefone pentachlorophenol pentoxazone
17 phenylmercury acetate pinoxaden prosulfalin pyribenzoxim pyriftalid guinoclamine rhodethanil sulglycapin thidiazimin tridiphane trimeturon tripropindan tritac Fungicides include, but are not limited to:
= aliphatic nitrogen fungicides butylamine cymoxanil dodicin dodine guazatine iminoctadine = amide fungicides carpropamid chloraniformethan cyflufenamid diclocymet ethaboxam fenoxanil flumetover furametpyr mandipropamid penthiopyrad prochloraz guinazamid silthiofam triforine = acylamino acid fungicides benalaxyl benalaxvl-M
furalaxyl metalaxyl metalaxyl-M
pefurazoate = anilide fungicides benalaxyl
= aliphatic nitrogen fungicides butylamine cymoxanil dodicin dodine guazatine iminoctadine = amide fungicides carpropamid chloraniformethan cyflufenamid diclocymet ethaboxam fenoxanil flumetover furametpyr mandipropamid penthiopyrad prochloraz guinazamid silthiofam triforine = acylamino acid fungicides benalaxyl benalaxvl-M
furalaxyl metalaxyl metalaxyl-M
pefurazoate = anilide fungicides benalaxyl
18 benalaxyl-M
boscalid carboxin fenhexamid metalaxyl metalaxyl-M
metsulfovax ofurace oxadixyl oxycarboxin pyracarbolid thifluzamide tiadinil = benzanilide fungicides benodanil flutolanil mebenil mepronil salicylanilide tecloftalam = furanilide fungicides fenfuram furalaxyl furcarbanil methfuroxam = sulfonanilide fungicides flusulfamide = benzamide fungicides benzohydroxamic acid fluopicolide tioxymid trichlamide zarilamid zoxamide = furamide fungicides cyclafuramid furmecyclox = phenylsulfamide fungicides dichiofluanid tolylfluanid = sulfonamide fungicides amisulbrom cyazofamid = valinamide fungicides benthiavalicarb iprovalicarb
boscalid carboxin fenhexamid metalaxyl metalaxyl-M
metsulfovax ofurace oxadixyl oxycarboxin pyracarbolid thifluzamide tiadinil = benzanilide fungicides benodanil flutolanil mebenil mepronil salicylanilide tecloftalam = furanilide fungicides fenfuram furalaxyl furcarbanil methfuroxam = sulfonanilide fungicides flusulfamide = benzamide fungicides benzohydroxamic acid fluopicolide tioxymid trichlamide zarilamid zoxamide = furamide fungicides cyclafuramid furmecyclox = phenylsulfamide fungicides dichiofluanid tolylfluanid = sulfonamide fungicides amisulbrom cyazofamid = valinamide fungicides benthiavalicarb iprovalicarb
19 = antibiotic fungicides aureofungin blasticidin-S
cycloheximide griseofulvin kasugamycin natamycin polyoxins polyoxorim streptomycin validamycin = strobilurin fungicides azoxystrobin dimoxystrobin fluoxastrobin kresoxim-methyl metominostrobin orysastrobin picoxystrobin pyraclostrobin trifloxystrobin = aromatic fungicides biphenyl chlorodinitronaphthalene chloroneb chiorothalonil cresol dicloran hexachlorobenzene pentachlorophenol quintozene sodium pentachiorophenoxide tecnazene = benzimidazole fungicides benomyl carbendazim chlorfenazole cypendazole debacarb fuberidazole mecarbinzid rabenzazole thiabendazole = benzimidazole precursor fungicides furophanate thiophanate thiophanate-methyl = benzothiazole fungicides bentaluron chlobenthiazone TCMTB
5 = bridged diphenyl fungicides bithionol dichlorophen diphenylamine = carbamate fungicides 10 benthiavalicarb furophanate iprovalicarb propamocarb thiophanate 15 thiophanate-methyl = benzimidazolylcarbamate fungicides benomyl carbendazim cypendazole
cycloheximide griseofulvin kasugamycin natamycin polyoxins polyoxorim streptomycin validamycin = strobilurin fungicides azoxystrobin dimoxystrobin fluoxastrobin kresoxim-methyl metominostrobin orysastrobin picoxystrobin pyraclostrobin trifloxystrobin = aromatic fungicides biphenyl chlorodinitronaphthalene chloroneb chiorothalonil cresol dicloran hexachlorobenzene pentachlorophenol quintozene sodium pentachiorophenoxide tecnazene = benzimidazole fungicides benomyl carbendazim chlorfenazole cypendazole debacarb fuberidazole mecarbinzid rabenzazole thiabendazole = benzimidazole precursor fungicides furophanate thiophanate thiophanate-methyl = benzothiazole fungicides bentaluron chlobenthiazone TCMTB
5 = bridged diphenyl fungicides bithionol dichlorophen diphenylamine = carbamate fungicides 10 benthiavalicarb furophanate iprovalicarb propamocarb thiophanate 15 thiophanate-methyl = benzimidazolylcarbamate fungicides benomyl carbendazim cypendazole
20 debacarb mecarbinzid = carbanilate fungicides diethofencarb = conazole fungicides = conazole fungicides (imidazoles) climbazole clotrimazole imazalil oxpoconazole prochloraz triflumizole see also imidazole fungicides = conazole fungicides (triazoles) azaconazole bromuconazole cyproconazole diclobutrazol difenoconazole diniconazole diniconazole-M
epoxiconazole etaconazole fenbuconazole fluguinconazole flusilazole flutriafol furconazole
epoxiconazole etaconazole fenbuconazole fluguinconazole flusilazole flutriafol furconazole
21 furconazole-cis hexaconazole imibenconazole ipconazole metconazole myclobutanil penconazole propiconazole prothioconazole quinconazole simeconazole tebuconazole tetraconazole triadimefon triadimenol triticonazole uniconazole uniconazole-P
see also triazole fungicides = copper fungicides Bordeaux mixture Burgundy mixture Cheshunt mixture copper acetate copper carbonate, basic copper hydroxide copper naphthenate copper oleate copper oxychloride copper sulfate copper sulfate, basic copper zinc chromate cufraneb cuprobam cuprous oxide mancopper oxine copper = dicarboximide fungicides famoxadone fluoroimide = dichlorophenyl dicarboximide fungicides chlozolinate dichlozoline iprodione isovaledione myclozolin
see also triazole fungicides = copper fungicides Bordeaux mixture Burgundy mixture Cheshunt mixture copper acetate copper carbonate, basic copper hydroxide copper naphthenate copper oleate copper oxychloride copper sulfate copper sulfate, basic copper zinc chromate cufraneb cuprobam cuprous oxide mancopper oxine copper = dicarboximide fungicides famoxadone fluoroimide = dichlorophenyl dicarboximide fungicides chlozolinate dichlozoline iprodione isovaledione myclozolin
22 procymidone vinclozolin = phthalimide fungicides captafol captan ditalimfos folpet thiochlorfenphim = dinitrophenol fungicides binapacryl dinobuton dinocap dinocap-4 dinocap-6 dinocton dinopenton dinosulfon dinoterbon DNOC
= dithiocarbamate fungicides azithiram carbamorph cufraneb cuprobam disulfiram ferbam metam nabam tecoram thiram ziram = cyclic dithiocarbamate fungicides dazomet etem milneb = polymeric dithiocarbamate fungicides mancopper mancozeb maneb metiram polycarbamate propineb zineb = imidazole fungicides cyazofamid fenamidone fenapanil
= dithiocarbamate fungicides azithiram carbamorph cufraneb cuprobam disulfiram ferbam metam nabam tecoram thiram ziram = cyclic dithiocarbamate fungicides dazomet etem milneb = polymeric dithiocarbamate fungicides mancopper mancozeb maneb metiram polycarbamate propineb zineb = imidazole fungicides cyazofamid fenamidone fenapanil
23 glyodin iprodione isovaledione pefurazoate triazoxide see also conazole fungicides ides (imidazoles) = inorganic fungicides potassium azide potassium thiocyanate sodium azide sulfur see also copper fungicides see also inorganic mercury fungicides = mercury fungicides = inorganic mercury fungicides mercuric chloride mercuric oxide mercurous chloride = organomercury fungicides (3-ethoxypropyl)mercury bromide ethvlmercury acetate ethvlmercury bromide ethylmercury chloride ethylmercury 2,3-dihydroxypropyl mercaptide ethylmercury phosphate N-(ethylmercurv)-p-toluenesulphonanilide hydrargaphen 2-methoxyethylmercury chloride methylmercury benzoate methylmercury dicyandiamide methylmercury pentachlorophenoxide 8-phenylmercurioxyguinoline phenylmercuriurea phenylmercury acetate phenylmercury chloride phenylmercury derivative of pyrocatechol phenylmercury nitrate phenylmercury salicylate thiomersal tolylmercury acetate = morpholine fungicides aldimorph benzamorf carbamorph dimethomorph dodemorph fenpropimorph
24 flumorph tridemorph = organophosphorus fungicides ampropylfos ditalimfos edifenphos fosetyl hexylthiofos iprobenfos phosdiphen pyrazophos tolclofos-methyl triamiphos = organotin fungicides decafentin fentin tributyltin oxide = oxathiin fungicides carboxin oxycarboxin = oxazole fungicides chlozolinate dichiozoline drazoxolon famoxadone hymexazol metazoxolon myclozolin oxad ixyl vinclozolin = polysulfide fungicides barium polysulfide calcium polysulfide potassium polysulfide sodium polysulfide = pyrazole fungicides furametpyr penthiopyrad = pyridine fungicides boscalid buthiobate dipyrithione fluazinam fluopicolide pyridinitril pyrifenox pyroxychlor rox ur = pyrimidine fungicides bupirimate 5 cyprodinil diflumetorim dimethirimol ethirimol fenarimol 10 ferimzone mepanipyrim nuarimol pyrimethanil triarimol 15 = pyrrole fungicides fenpiclonil fludioxonil fluoroimide = quinoline fungicides 20 ethoxyguin halacrinate 8-hydroxy uinoline sulfate guinacetol guinoxyfen
25 = quinone fungicides benguinox chloranil dichlone dithianon = quinoxaline fungicides chinomethionat chlorquinox thioquinox = thiazole fungicides ethaboxam etridiazole metsulfovax octhilinone thiabendazole thiadifluor thifluzamide = thiocarbamate fungicides methasulfocarb prothiocarb = thiophene fungicides ethaboxam silthiofam
26 = triazine fungicides anilazine = triazole fungicides amisulbrom bitertanol fluotrimazole triazbutil see also conazole fungicides (triazoles) = urea fungicides bentaluron pencycuron guinazamid = unclassified fungicides acibenzolar acypetacs allyl alcohol benzalkonium chloride benzamacril bethoxazin carvone chloropicrin DBCP
dehydroacetic acid diclomezine diethyl pyrocarbonate fenaminosulf fenitropan fenpropidin formaldehyde furfural hexachlorobutadiene iodomethane isoprothiolane methyl bromide methyl isothiocyanate metrafenone nitrostyrene nitrothal-isopropyl OCH
2-phenylphenol phthalide piperalin probenazole proquinazid pyroquilon sodium orthophenylphenoxide spiroxamine
dehydroacetic acid diclomezine diethyl pyrocarbonate fenaminosulf fenitropan fenpropidin formaldehyde furfural hexachlorobutadiene iodomethane isoprothiolane methyl bromide methyl isothiocyanate metrafenone nitrostyrene nitrothal-isopropyl OCH
2-phenylphenol phthalide piperalin probenazole proquinazid pyroquilon sodium orthophenylphenoxide spiroxamine
27 sultropen thicyofen tricyclazole zinc naphthenate Insecticides include, but are not limited to:
= antibiotic insecticides allosamidin thuringiensin o macrocyclic lactone insecticides spinosad = avermectin insecticides abamectin doramectin emamectin eprinomectin ivermectin selamectin = milbemycin insecticides lepimectin milbemectin milbemycin oxime moxidectin = arsenical insecticides calcium arsenate copper acetoarsenite copper arsenate lead arsenate potassium arsenite sodium arsenite = botanical insecticides anabasine azadirachtin d-limonene nicotine pyrethrins cinerins cinerin I
cinerin II
jasmolin I
iasmolin II
pyrethrin I
= antibiotic insecticides allosamidin thuringiensin o macrocyclic lactone insecticides spinosad = avermectin insecticides abamectin doramectin emamectin eprinomectin ivermectin selamectin = milbemycin insecticides lepimectin milbemectin milbemycin oxime moxidectin = arsenical insecticides calcium arsenate copper acetoarsenite copper arsenate lead arsenate potassium arsenite sodium arsenite = botanical insecticides anabasine azadirachtin d-limonene nicotine pyrethrins cinerins cinerin I
cinerin II
jasmolin I
iasmolin II
pyrethrin I
28 pyrethrin II
quassia rotenone ryania sabadilla = carbamate insecticides bendiocarb carbaryl o benzofuranyl methylcarbamate insecticides benfuracarb carbofuran carbosulfan decarbofuran furathiocarb o dimethylcarbamate insecticides dimetan dimetilan hyquincarb pirimicarb o oxime carbamate insecticides alanycarb aidicarb aldoxycarb butocarboxim butoxycarboxim methomyl nitrilacarb oxamyl tazimcarb thiocarboxime thiodicarb thiofanox o phenyl methylcarbamate insecticides allyxycarb aminocarb bufencarb butacarb carbanolate cloethocarb dicresyl dioxacarb EMPC
ethiofencarb fenethacarb
quassia rotenone ryania sabadilla = carbamate insecticides bendiocarb carbaryl o benzofuranyl methylcarbamate insecticides benfuracarb carbofuran carbosulfan decarbofuran furathiocarb o dimethylcarbamate insecticides dimetan dimetilan hyquincarb pirimicarb o oxime carbamate insecticides alanycarb aidicarb aldoxycarb butocarboxim butoxycarboxim methomyl nitrilacarb oxamyl tazimcarb thiocarboxime thiodicarb thiofanox o phenyl methylcarbamate insecticides allyxycarb aminocarb bufencarb butacarb carbanolate cloethocarb dicresyl dioxacarb EMPC
ethiofencarb fenethacarb
29 fenobucarb isoprocarb methiocarb metolcarb mexacarbate promacyl promecarb propoxur trimethacarb XMC
xylylcarb = dinitrophenol insecticides dinex dinoprop dinosam DNOC
= fluorine insecticides barium hexafluorosilicate cryolite sodium fluoride sodium hexafluorosilicate suIfluramid = formamidine insecticides amitraz chlordimeform formetanate formparanate = fumigant insecticides acrylonitrile carbon disulfide carbon tetrachloride chloroform chloropicrin Para-dichlorobenzene 1,2-dichloropropane ethyl formate ethylene dibromide ethylene dichloride ethylene oxide hydrogen cyanide iodomethane methyl bromide methylchloroform methylene chloride naphthalene phosphine sulfuryl fluoride tetrachloroethane 5 = inorganic insecticides borax calcium polysulfide copper oleate mercurous chloride 10 potassium thiocyanate sodium thiocyanate see also arsenical insecticides see also fluorine insecticides = insect growth regulators 15 o chitin synthesis inhibitors bistrifluron buprofezin chlorfluazuron cyromazine 20 diflubenzuron flucycloxuron flufenoxuron hexaflumuron lufenuron 25 novaluron noviflumuron penfluron teflubenzuron triflumuron
xylylcarb = dinitrophenol insecticides dinex dinoprop dinosam DNOC
= fluorine insecticides barium hexafluorosilicate cryolite sodium fluoride sodium hexafluorosilicate suIfluramid = formamidine insecticides amitraz chlordimeform formetanate formparanate = fumigant insecticides acrylonitrile carbon disulfide carbon tetrachloride chloroform chloropicrin Para-dichlorobenzene 1,2-dichloropropane ethyl formate ethylene dibromide ethylene dichloride ethylene oxide hydrogen cyanide iodomethane methyl bromide methylchloroform methylene chloride naphthalene phosphine sulfuryl fluoride tetrachloroethane 5 = inorganic insecticides borax calcium polysulfide copper oleate mercurous chloride 10 potassium thiocyanate sodium thiocyanate see also arsenical insecticides see also fluorine insecticides = insect growth regulators 15 o chitin synthesis inhibitors bistrifluron buprofezin chlorfluazuron cyromazine 20 diflubenzuron flucycloxuron flufenoxuron hexaflumuron lufenuron 25 novaluron noviflumuron penfluron teflubenzuron triflumuron
30 o juvenile hormone mimics epofenonane fenoxycarb hydroprene kinoprene methoprene pyriproxyfen triprene o juvenile hormones juvenile hormone I
juvenile hormone II
juvenile hormone III
o moulting hormone agonists chromafenozide
juvenile hormone II
juvenile hormone III
o moulting hormone agonists chromafenozide
31 halofenozide methoxyfenozide tebufenozide o moulting hormones a-ecdysone ecdysterone o moulting inhibitors diofenolan o precocenes precocene precocene II
precocene III
o unclassified insect growth regulators dic coil = nereistoxin analogue insecticides bensultap cartap thiocyclam thiosultap = nicotinoid insecticides flonicamid o nitroguanidine insecticides clothianidin dinotefuran imidacloprid thiamethoxam o nitromethylene insecticides nitenpyram nithiazine o pyridylmethylamine insecticides acetamiprid imidacloprid nitenpyram thiacloprid = organochlorine insecticides bromo-DDT
camphechlor DDT
pp'-DDT
ethyl-DDD
precocene III
o unclassified insect growth regulators dic coil = nereistoxin analogue insecticides bensultap cartap thiocyclam thiosultap = nicotinoid insecticides flonicamid o nitroguanidine insecticides clothianidin dinotefuran imidacloprid thiamethoxam o nitromethylene insecticides nitenpyram nithiazine o pyridylmethylamine insecticides acetamiprid imidacloprid nitenpyram thiacloprid = organochlorine insecticides bromo-DDT
camphechlor DDT
pp'-DDT
ethyl-DDD
32 HCH
gamma-HCH
lindane methoxychlor pentachlorophenol TDE
o cyclodiene insecticides aidrin bromocyclen chlorbicyclen chlordane chiordecone dieidrin dilor endosulfan endrin HEOD
heptachlor HHDN
isobenzan isodrin kelevan mirex = organophosphorus insecticides o organophosphate insecticides bromfenvinfos chiorfenvinphos crotoxyphos dichiorvos dicrotophos dimethylvinphos fospirate heptenophos methocrotophos mevinphos monocrotophos naled naftalofos phosphamidon propaphos TEPP
tetrachlorvinphos o organothiophosphate insecticides dioxabenzofos
gamma-HCH
lindane methoxychlor pentachlorophenol TDE
o cyclodiene insecticides aidrin bromocyclen chlorbicyclen chlordane chiordecone dieidrin dilor endosulfan endrin HEOD
heptachlor HHDN
isobenzan isodrin kelevan mirex = organophosphorus insecticides o organophosphate insecticides bromfenvinfos chiorfenvinphos crotoxyphos dichiorvos dicrotophos dimethylvinphos fospirate heptenophos methocrotophos mevinphos monocrotophos naled naftalofos phosphamidon propaphos TEPP
tetrachlorvinphos o organothiophosphate insecticides dioxabenzofos
33 fosmethilan phenthoate = aliphatic organothiophosphate insecticides acethion amiton cadusafos chlorethoxyfos chiormephos demephion demephion-O
demephion-S
demeton demeton-O
demeton-S
demeton-methyl demeton-O-methyl demeton-S-methyl demeton-S-methylsulphon disulfoton ethion ethoprophos IPSP
isothioate malathion methacrifos oxydemeton-methyl oxydeprofos oxydisulfoton hp orate sulfotep terbufos thiometon = aliphatic amide organothiophosphate insecticides amidithion cyanthoate dimethoate ethoate-methyl formothion mecarbam omethoate prothoate sophamide vamidothion
demephion-S
demeton demeton-O
demeton-S
demeton-methyl demeton-O-methyl demeton-S-methyl demeton-S-methylsulphon disulfoton ethion ethoprophos IPSP
isothioate malathion methacrifos oxydemeton-methyl oxydeprofos oxydisulfoton hp orate sulfotep terbufos thiometon = aliphatic amide organothiophosphate insecticides amidithion cyanthoate dimethoate ethoate-methyl formothion mecarbam omethoate prothoate sophamide vamidothion
34 = oxime organothiophosphate insecticides chlorphoxim phoxim phoxim-methyl = heterocyclic organothiophosphate insecticides azamethiphos coumaphos coumithoate dioxathion endothion menazon morphothion phosalone pyraclofos pyridaphenthion guinothion = benzothiopyran organothiophosphate insecticides dithicrofos thicrofos = benzotriazine organothiophosphate insecticides azinphos-ethyl azinphos-methyl = isoindole organothiophosphate insecticides dialifos phosmet = isoxazole organothiophosphate insecticides isoxathion zolaprofos = pyrazolopyrimidine organothiophosphate insecticides chiorprazophos pyrazophos = pyridine organothiophosphate insecticides chlorpyrifos ch lorpyrifos-m ethyl = pyrimidine organothiophosphate insecticides butathiofos diazinon etrimfos lirimfos pirimiphos-ethyl pirimiphos-methyl primidophos pyrimitate 5 tebupirimfos = quinoxaline organothiophosphate insecticides quinaiphos quinaiphos-methyl = thiadiazole organothiophosphate insecticides 10 athidathion lythidathion methidathion prothidathion = triazole organothiophosphate insecticides 15 isazofos triazophos = phenyl organothiophosphate insecticides azothoate bromophos 20 bromophos-ethyl carbophenothion chlorthiophos cyanophos c hioate 25 dicapthon dichlofenthion etaphos famphur fenchlorphos 30 fenitrothion fensulfothion fenthion fenthion-ethyl heterophos
35 jodfenphos mesulfenfos parathion parathion-methyl phenkapton phosnichlor profenofos prothiofos sulprofos temephos
36 trichlormetaphos-3 trifenofos o phosphonate insecticides butonate trichlorfon o phosphonothioate insecticides mecarphon = phenyl ethylphosphonothioate insecticides fonofos trichloronat = phenyl phenylphosphonothioate insecticides cyanofenphos EPN
leptophos o phosphoramidate insecticides crufomate fenamiphos fosthietan mephosfolan phosfolan pirimetaphos o phosphoramidothioate insecticides acephate isocarbophos isofenphos methamidophos propetamphos o phosphorodiamide insecticides dimefox mazidox mipafox schradan = oxadiazine insecticides indoxacarb = phthalimide insecticides dialifos phosmet tetramethrin = pyrazole insecticides acetoprole
leptophos o phosphoramidate insecticides crufomate fenamiphos fosthietan mephosfolan phosfolan pirimetaphos o phosphoramidothioate insecticides acephate isocarbophos isofenphos methamidophos propetamphos o phosphorodiamide insecticides dimefox mazidox mipafox schradan = oxadiazine insecticides indoxacarb = phthalimide insecticides dialifos phosmet tetramethrin = pyrazole insecticides acetoprole
37 ethiprole fipronil pyrafluprole pyriprole tebufenpyrad tolfenpyrad vaniliprole = pyrethroid insecticides o pyrethroid ester insecticides acrinathrin allethrin bioallethrin barthrin bifenthrin bioethanomethrin cyclethrin cycloprothrin cyfluthrin beta-cyfluthrin cyhalothrin gamma-cyhalothrin lambda-cyhalothrin cypermethrin alpha-cypermethrin beta-cypermethrin theta-cypermethrin zeta-cypermethrin cyphenothrin deltamethrin dimefluthrin dimethrin empenthrin fenfluthrin fenpirithrin fenpropathrin fenvalerate esfenvalerate flucythrinate fluvalinate tau-fluvalinate furethrin imiprothrin metofluthrin permethrin biopermethrin transpermethrin
38 phenothrin prallethrin profluthrin pyres m eth ri n resmethrin bioresmethrin cismethrin tefluthrin terallethrin tetram eth ri n tral ometh ri n transfluthrin o pyrethroid ether insecticides etofenprox flufenprox halfenprox protrifenbute silafluofen = pyrimidinamine insecticides flufenerim pyrimidifen = pyrrole insecticides chlorfenapyr = tetronic acid insecticides spiromesifen spirotetramat = thiourea insecticides diafenthiuron = urea insecticides flucofuron sulcofuron see also chitin synthesis inhibitors = unclassified insecticides closantel crotamiton EXD
fenazaflor fenoxacrim flubendiamide hydramethylnon isoprothiolane malonoben
fenazaflor fenoxacrim flubendiamide hydramethylnon isoprothiolane malonoben
39 metaflumizone metoxadiazone nifluridide pyridaben rpy idalyl rafoxanide triarathene triazamate Plant growth regulators include, but are not limited to:
= antiauxins clofibric acid 2 3 5-tri-iodobenzoic acid = auxins 2,4-D
2,4-DB
2,4-DEP
dichlorprop fenoprop IAA
IBA
naphthaleneacetamide a-naphthaleneacetic acid 1-naphthol naphthoxyacetic acid potassium naphthenate sodium naphthenate 2,4,5-T
= cytokinins 2iP
benzyladenine kinetin zeatin = defoliants calcium cyanamide dimethipin endothal ethephon merphos metoxuron pentachlorophenol thidiazuron tribufos = ethylene inhibitors avigl cine 1-methylcyclopropene = ethylene releasers etacelasil ethephon gl oy xime = gibberellins 10 gibberellins gibberellic acid = growth inhibitors abscisic acid ancymidol 15 butralin carbaryl chlorphonium chlorpropham lac dikegulac 20 flumetralin fluoridamid fosamine glyphosine isopyrimol 25 iasmonic acid maleic hydrazide mepiguat piproctanyl prohydrojasmon 30 propham 2,3,5-tri-iodobenzoic acid o morphactins chlorfluren chlorflurenol 35 dichlorflurenol flurenol = growth retardants chlormeguat daminozide
= antiauxins clofibric acid 2 3 5-tri-iodobenzoic acid = auxins 2,4-D
2,4-DB
2,4-DEP
dichlorprop fenoprop IAA
IBA
naphthaleneacetamide a-naphthaleneacetic acid 1-naphthol naphthoxyacetic acid potassium naphthenate sodium naphthenate 2,4,5-T
= cytokinins 2iP
benzyladenine kinetin zeatin = defoliants calcium cyanamide dimethipin endothal ethephon merphos metoxuron pentachlorophenol thidiazuron tribufos = ethylene inhibitors avigl cine 1-methylcyclopropene = ethylene releasers etacelasil ethephon gl oy xime = gibberellins 10 gibberellins gibberellic acid = growth inhibitors abscisic acid ancymidol 15 butralin carbaryl chlorphonium chlorpropham lac dikegulac 20 flumetralin fluoridamid fosamine glyphosine isopyrimol 25 iasmonic acid maleic hydrazide mepiguat piproctanyl prohydrojasmon 30 propham 2,3,5-tri-iodobenzoic acid o morphactins chlorfluren chlorflurenol 35 dichlorflurenol flurenol = growth retardants chlormeguat daminozide
40 flurprimidol mefluidide paclobutrazol tetcyclacis uniconazole
41 = growth stimulators brassinolide forchlorfenuron hymexazol = unclassified plant growth regulators benzofluor buminafos carvone ciobutide clofencet cloxyfonac cyclanilide cycloheximide epocholeone ethychlozate ethylene fenridazon heptopargil holosulf inabenfide karetazan lead arsenate methasulfocarb prohexadione pydanon sintofen triapenthenol trinexapac The adjuvant of the invention comprises phosphated 2-propylheptanol and/or a phosphated 2-propylheptanol alkoxylate, where the alkoxylate on average comprises 1-20, in another embodiment 2-10, in still another embodiment 2-6, and in still another embodiment 2-4, and most preferably 3, ethyleneoxy units and 0-3, preferably 0-2, propyleneoxy units.
In one embodiment, the adjuvant of the invention comprises at least one phosphated alkoxylate according to the formula OM
H3C-(-CH-4CH-CHZ O+CHZ CH2 u-P-OM (II)
In one embodiment, the adjuvant of the invention comprises at least one phosphated alkoxylate according to the formula OM
H3C-(-CH-4CH-CHZ O+CHZ CH2 u-P-OM (II)
42 where M is H, a monovalent metal ion or R1R2R3R4N+, where R1, R2, R3, and R4 are H, an alkyl group with 1-4 carbon atoms or -CH2CH2OH, and c is a number 1-20, preferably 2-10, more preferably 2-6, even more preferably 2-4, and most preferably 3.
Phosphated 2-propyiheptanol or a phosphated 2-propylheptanol alkoxylate may be obtained by different processes, the most common being the reaction of 2-propylheptanol or alkoxylated 2-propylheptanol with polyphosphoric acid or phosphorous pentoxide (P205)-In the process using polyphosphoric acid the resulting product mixture will predominantly contain the monoalkylphosphate ester of 2-propylheptanol or of alkoxylated 2-propylheptanol and only a small amount (<10%) of the dial kylphosphate ester. Always rather large amounts of inorganic phosphate residues from the polyphosphoric acid, such as orthophosphoric acid, will be present.
When P205 is used as the phosphatising reagent and the molar ratio between P205 and alcohol or alkoxylated alcohol is 1:3, the product mixture will contain about equal amounts of monoalkylphosphate ester and dialkylphosphate ester, and only smaller amounts of inorganic phosphate residues. A larger amount of alcohol or alkoxylated alcohol will yield more diester, and a smaller amount will yield more monoester. It will be known to a person skilled in the art how to synthesise phosphate esters with certain amounts of mono- and dialkyl phosphate esters. For a general description of phosphate esters see, e.g., Anionic Surfactants Vol. 7, Part 11, pages 504-511 in Surfactant Science Series, edited by Warner M. Linfield, Marcel Dekker Inc., New York and Basle 1976. The alcohol alkoxylates to be phosphated may be either of the standard type produced by using an alkaline catalyst such as KOH, or of the narrow range type produced by using a narrow range catalyst, such as an acid catalyst, Ca(OH)2 or hydrotalcite.
Phosphated 2-propyiheptanol or a phosphated 2-propylheptanol alkoxylate may be obtained by different processes, the most common being the reaction of 2-propylheptanol or alkoxylated 2-propylheptanol with polyphosphoric acid or phosphorous pentoxide (P205)-In the process using polyphosphoric acid the resulting product mixture will predominantly contain the monoalkylphosphate ester of 2-propylheptanol or of alkoxylated 2-propylheptanol and only a small amount (<10%) of the dial kylphosphate ester. Always rather large amounts of inorganic phosphate residues from the polyphosphoric acid, such as orthophosphoric acid, will be present.
When P205 is used as the phosphatising reagent and the molar ratio between P205 and alcohol or alkoxylated alcohol is 1:3, the product mixture will contain about equal amounts of monoalkylphosphate ester and dialkylphosphate ester, and only smaller amounts of inorganic phosphate residues. A larger amount of alcohol or alkoxylated alcohol will yield more diester, and a smaller amount will yield more monoester. It will be known to a person skilled in the art how to synthesise phosphate esters with certain amounts of mono- and dialkyl phosphate esters. For a general description of phosphate esters see, e.g., Anionic Surfactants Vol. 7, Part 11, pages 504-511 in Surfactant Science Series, edited by Warner M. Linfield, Marcel Dekker Inc., New York and Basle 1976. The alcohol alkoxylates to be phosphated may be either of the standard type produced by using an alkaline catalyst such as KOH, or of the narrow range type produced by using a narrow range catalyst, such as an acid catalyst, Ca(OH)2 or hydrotalcite.
43 If necessary, the reaction mixture resulting from either of the procedures can be neutralized by an organic or inorganic base before use. The base may be, e.g., an alkali hydroxide, such as sodium hydroxide or potassium hydroxide; ammonia, an alkanolamine, such as monoethanolamine, triethanolamine or methyldiethanolamine; or an alkylamine such as triethylamine.
The monoalkylphosphate ester of 2-propylheptanol or of ethoxylated 2-propylheptanol has the formula OM
H3C4-GH2--4CH-CH2 O+CH2 CH20-}c P-OM (II) where M is H, a monovalent metal ion or R1R2R3R4N+, where R1, R2, R3, and R4 are H, an alkyl group with 1-4 carbon atoms or -CH2CH2OH, and c is a number 0-20, preferably 2-10, more preferably 2-6, even more preferably 2-4, and most preferably 3. The product mixture resulting from the reaction of 2-propylheptanol or of ethoxylated 2-propylheptanol with polyphosphoric acid may also contain smaller amounts of products containing more than one phosphate unit according to the formula OM
H3C-tCHCH-j4-CH2 CHO-I-tO-M (III) where n is 1-3 and M and c have the same meaning as above.
For ethoxylates containing smaller amounts of ethyleneoxy units, also a certain amount of unethoxylated product will remain due to the distribution of ethyleneoxy units. This unethoxylated product will also be phosphatised during the reaction with the phosphatising agent, and thus the phosphate ester of 2-propylheptanol will also be present in the reaction mixture resulting from these above-mentioned ethoxylates.
The dialkylphosphate ester of 2-propylheptanol has the formula
The monoalkylphosphate ester of 2-propylheptanol or of ethoxylated 2-propylheptanol has the formula OM
H3C4-GH2--4CH-CH2 O+CH2 CH20-}c P-OM (II) where M is H, a monovalent metal ion or R1R2R3R4N+, where R1, R2, R3, and R4 are H, an alkyl group with 1-4 carbon atoms or -CH2CH2OH, and c is a number 0-20, preferably 2-10, more preferably 2-6, even more preferably 2-4, and most preferably 3. The product mixture resulting from the reaction of 2-propylheptanol or of ethoxylated 2-propylheptanol with polyphosphoric acid may also contain smaller amounts of products containing more than one phosphate unit according to the formula OM
H3C-tCHCH-j4-CH2 CHO-I-tO-M (III) where n is 1-3 and M and c have the same meaning as above.
For ethoxylates containing smaller amounts of ethyleneoxy units, also a certain amount of unethoxylated product will remain due to the distribution of ethyleneoxy units. This unethoxylated product will also be phosphatised during the reaction with the phosphatising agent, and thus the phosphate ester of 2-propylheptanol will also be present in the reaction mixture resulting from these above-mentioned ethoxylates.
The dialkylphosphate ester of 2-propylheptanol has the formula
44 OM
O-CHZ CH O-CH2 CH-{-CHI-CH3 (IV) H3C-(-CH2-)-4CH-CH2 -O--FCHZCHZ O*IPI' where M and c have the same meaning as above. The product mixture resulting from the reaction of 2-propylheptanol or ethoxylated 2-propylheptanol with may also contain a dialkyl diphosphate ester according to the formula OM OM
H3C-ECHZ }4-CH-CH2 O--CHZ CH2 O IPI-O-IPI---O-CHI CH O-CH- CH+CH CH3 (V) where M and c have the same meaning as above. This type of diester may be hydrolysed to yield 2 moles of monoester.
2-Propylheptanol is normally made by a process resulting in small amounts of by-products such as 4-methyl-2-propylhexanol and 5-methyl-2-propylhexanol. These products or their ethoxylates will also be phosphated during the process, and the phosphated species will be comprised in the resulting product mixture.
The reaction mixtures obtained by the phosphatising procedures are normally used as such without any purification procedure, but both the mixtures and the purified phosphate esters function as hydrotropes. To act as a good hydrotrope, the mixture should predominantly contain the monoalkyl phosphate esters, since these are better hydrotropes than the dialkyl phosphate esters.
Preferably more than 60, more preferably more than 70, and most preferably more than 80% by weight of the mixture should be monoalkyl phosphate esters.
The phosphated 2-propylheptanol or phosphated 2-propylheptanol alkoxylates where the alkoxylate on average comprises 1-20, preferably 2-10, more preferably 2-6, even more preferably 2-4, and most preferably 3, ethyleneoxy units and 0-3, preferably 0-2, propyleneoxy and/or butyleneoxy, preferably propyleneoxy, units described above and a process for their production are already partly disclosed in the earlier mentioned publications EP-A-256427 and CH-A-481953 for use as dispersants for pigments and as additives in an emulsion polymerisation process, respectively. However, the 5 phosphated 2-propylheptanol alkoxylate where the alkoxylate comprises 2-4, preferably 3, ethyleneoxy units on average is especially efficient as a hydrotrope compared to the other phosphated alkoxylates of 2-propylheptanol (see Table I in the Examples). Therefore, the invention also relates to the phosphated 2-propylheptanol alkoxylate where the alkoxylate on average 10 comprises 2-4, preferably 3, ethyleneoxy units per se and a process for its production.
The agricultural formulations of the invention may contain alkali, preferably sodium or potassium hydroxide, and an alkaline complexing agent 15 that may be inorganic as well as organic. Typical examples of inorganic complexing agents used in the alkaline composition are alkali salts of silicates and phosphates such as sodium silicate, sodium metasilicate, sodium tripolyphosphate, sodium orthophosphate, sodium pyrophosphate, and the corresponding potassium salts. Typical examples of organic complexing agents 20 are alkaline aminopolyphosphonates, organic phosphates, polycarboxylates, such as citrates; aminocarboxylates, such as sodium nitrilotriacetate (Na3NTA), sodium ethylenediaminetetraacetate (EDTA), sodium diethylenetriaminepentaacetate, sodium 1,3-propylenediaminetetraacetate, and sodium hydroxyethylethylenediaminetriacetate. The amount of alkali present in 25 the composition depends on the application and on whether the composition is a concentrate or a ready-to-use solution.
The concentrated compositions of the present invention are stable and in many cases generally clear. The clarity interval is suitably between 0-30 40 C, preferably between 0-50 C, and most preferably between 0-60 C. This may be adapted by changing the ratio of hydrotrope to nonionic surfactant. The concentrate normally contains 50-95% by weight of water, suitably 70-90% by weight.
To obtain a ready-to-use solution the concentrates are diluted with water and/or fertilizer solutions up to 1:40. The diluted solutions are also clear and stable, but in some cases they may turn a little bit hazy although they are still stable and do not separate. The ready-to-use solutions exhibit good properties. A typical concentrate formulation contains 3-5% by weight of the adjuvant according to the present invention, while a ready-to-use formulation would normally contain 0.2-1 % by weight of same.
Tank mixes can include multiple pesticides mixed together, targeting multiple pests, while using water as the delivery medium. In that case the adjuvant would help prevent incompatibilities that could occur when mixing different formulation types together, such as emulsifiable concentrates and suspension concentrates.
Tank mixes can also include pesticide(s) dispersed or emulsified in a fertilizer solution. The adjuvants of the present invention function to facilitate the dispersion or emulsification of the pesticides(s) in the salt solutions by coupling the surfactants into the electrolyte solution.
The present invention is further illustrated by the following Examples.
Example 1 This example relates to a comparison between phosphated 2-propylheptanol +
5 EO and phosphated hexanol + 5 EO as hydrotropes for 2-propylheptanol + 5 EO.
Table 1 Formulation B
Compound Formulation A (Comparison) Phosphated 2-PH+5EO 3.5%
Phosphated 4.9%
hexanol+5EO
2-PH+5EO 5.0% 5.0%
Sodium metasilicate 4.0% 4.0%
Tetrapotassium 6.0% 6.0%
pyrophosphate Water 81.5% 80.1%
A smaller amount of phosphated 2-propylheptanol+5EO, as compared to phosphated hexanol+5EO, was required to obtain a clarity interval of 0-600C.
The formulations with phosphated 2-propylheptanol + 5 EO as a hydrotrope were also much more stable upon dilution.
Example 2 This example compares a number of phosphated ethoxylated alcohols with phosphated 2-propylheptanol + 5 EO as a hydrotrope for 2-propylheptanol + 5 EO.
Table 3 Compound 1 (Comparison) (Comparison) (Comparison) 2-PH+5EO 5.0% 5.0% 5.0% 5.0%
Phosphated 2- 3.5%
PH+5EO
Phosphated 3.0%
C9-CII-alcohol +5.5EO
Phosphated 3.4%
C9-C11-alcohol +4EO
Phosphated 2- 3.0%
ethyihexanol +4EO
Sodium 4.0 4.0 4.0 4.0 metasilicate Tetra- 6.0 6.0 6.0 6.0 potassium pyrophosphate Water 81.5 82.0 79.0 82.0 Table 4 Formu- Clarity Appearance Appearance Appearance Appearance Soil lation interval after dilution after dilution after dilution after dilution removal ( C) 1:5 after 1 1:20 after 1 1:5 after 1 1:20 after I at 1:20 day day week week dilution 1 0-70 Clear Clear Clear Hazy but 60.0 stable 2 0-53 Clear Clear Clear Clear 26.0 (COMP.) 3 0-60 Clear Clear Clear Clear 44.0 (Comp.) 4 0-50 Hazy Hazy Cloudy Hazy 54.0 (COMP.) The formulation according to the invention exhibited the best cleaning performance of all the investigated formulations, in combination with a good stability upon dilution.
Example 3 In this example the wetting ability of a composition according to the invention was measured by the modified Drave's test.
Table 5 Compound C
Phosphated 2-PH+5EO 6%
C9-Cll-alcohol+4EO 5.0%
Sodium nitrilotriacetate 10.0%
In the modified Drave's test, the sinking time in s is measured for a specified cotton yarn in approximately 0.1 % surfactant solution. The formulation in the Table 5 was diluted with distilled water to 0.1 % by weight with respect to the C9-C11-alcohol + 4 EO, and the modified Drave's test was performed on this solution. The result is displayed in the Table 6, below.
Table 6 Formulation Clarity interval pH Sinking time C (s) C 0-45 10.5 5 The formulation containing the phosphated 2-propylheptanol + 5 EO as a hydrotrope for the ethoxylate had a good wetting ability, whereas for the different components alone, the wetting time was >420 s. The C9-Cj -alcohol is not soluble in this alkaline medium without a hydrotrope, and the phosphated 2-propylheptanol + 5 EO has no good wetting ability on its own. When the hydrotrope is added, the nonionic surfactant is solubilised, and it is then able to exert its wetting ability.
Example 4 In the syntheses described below a 1,000 cm3 flange flask equipped with an anchor stirrer was used. The reactor was heated by an electrical heater equipped with a thermostat. A slight flow of nitrogen was applied during the 5 reaction. The polyphosphoric acid (PPA) used was Polyphosphoric acid 116, 84% equivalent in P205 (Albright & Wilson).
1) 2-propylheptanol + PPA
2-propylheptanol (222.47 g, 1.41 mole) was charged and heated to 45 C. PPA
10 (254.09 g) was added from a 60 ml syringe and the exothermic reaction was kept at 55-70 C while stirring at 240 r/min. PPA was added during a period of hour. The reaction was then left for 2 h at 60 C and with stirring at 300 r/min.
After the post-reaction water (5.0 g) was added to hydrolyse the remaining PPA, after which the acid was neutralised with KOH (274.4 g) dissolved in 555.0 g 15 water.
2) 2-propylheptanol + 3 EO +PPA
2-propylheptanol +3 EO (295.63 g, 1.02 mole) was charged and heated to
O-CHZ CH O-CH2 CH-{-CHI-CH3 (IV) H3C-(-CH2-)-4CH-CH2 -O--FCHZCHZ O*IPI' where M and c have the same meaning as above. The product mixture resulting from the reaction of 2-propylheptanol or ethoxylated 2-propylheptanol with may also contain a dialkyl diphosphate ester according to the formula OM OM
H3C-ECHZ }4-CH-CH2 O--CHZ CH2 O IPI-O-IPI---O-CHI CH O-CH- CH+CH CH3 (V) where M and c have the same meaning as above. This type of diester may be hydrolysed to yield 2 moles of monoester.
2-Propylheptanol is normally made by a process resulting in small amounts of by-products such as 4-methyl-2-propylhexanol and 5-methyl-2-propylhexanol. These products or their ethoxylates will also be phosphated during the process, and the phosphated species will be comprised in the resulting product mixture.
The reaction mixtures obtained by the phosphatising procedures are normally used as such without any purification procedure, but both the mixtures and the purified phosphate esters function as hydrotropes. To act as a good hydrotrope, the mixture should predominantly contain the monoalkyl phosphate esters, since these are better hydrotropes than the dialkyl phosphate esters.
Preferably more than 60, more preferably more than 70, and most preferably more than 80% by weight of the mixture should be monoalkyl phosphate esters.
The phosphated 2-propylheptanol or phosphated 2-propylheptanol alkoxylates where the alkoxylate on average comprises 1-20, preferably 2-10, more preferably 2-6, even more preferably 2-4, and most preferably 3, ethyleneoxy units and 0-3, preferably 0-2, propyleneoxy and/or butyleneoxy, preferably propyleneoxy, units described above and a process for their production are already partly disclosed in the earlier mentioned publications EP-A-256427 and CH-A-481953 for use as dispersants for pigments and as additives in an emulsion polymerisation process, respectively. However, the 5 phosphated 2-propylheptanol alkoxylate where the alkoxylate comprises 2-4, preferably 3, ethyleneoxy units on average is especially efficient as a hydrotrope compared to the other phosphated alkoxylates of 2-propylheptanol (see Table I in the Examples). Therefore, the invention also relates to the phosphated 2-propylheptanol alkoxylate where the alkoxylate on average 10 comprises 2-4, preferably 3, ethyleneoxy units per se and a process for its production.
The agricultural formulations of the invention may contain alkali, preferably sodium or potassium hydroxide, and an alkaline complexing agent 15 that may be inorganic as well as organic. Typical examples of inorganic complexing agents used in the alkaline composition are alkali salts of silicates and phosphates such as sodium silicate, sodium metasilicate, sodium tripolyphosphate, sodium orthophosphate, sodium pyrophosphate, and the corresponding potassium salts. Typical examples of organic complexing agents 20 are alkaline aminopolyphosphonates, organic phosphates, polycarboxylates, such as citrates; aminocarboxylates, such as sodium nitrilotriacetate (Na3NTA), sodium ethylenediaminetetraacetate (EDTA), sodium diethylenetriaminepentaacetate, sodium 1,3-propylenediaminetetraacetate, and sodium hydroxyethylethylenediaminetriacetate. The amount of alkali present in 25 the composition depends on the application and on whether the composition is a concentrate or a ready-to-use solution.
The concentrated compositions of the present invention are stable and in many cases generally clear. The clarity interval is suitably between 0-30 40 C, preferably between 0-50 C, and most preferably between 0-60 C. This may be adapted by changing the ratio of hydrotrope to nonionic surfactant. The concentrate normally contains 50-95% by weight of water, suitably 70-90% by weight.
To obtain a ready-to-use solution the concentrates are diluted with water and/or fertilizer solutions up to 1:40. The diluted solutions are also clear and stable, but in some cases they may turn a little bit hazy although they are still stable and do not separate. The ready-to-use solutions exhibit good properties. A typical concentrate formulation contains 3-5% by weight of the adjuvant according to the present invention, while a ready-to-use formulation would normally contain 0.2-1 % by weight of same.
Tank mixes can include multiple pesticides mixed together, targeting multiple pests, while using water as the delivery medium. In that case the adjuvant would help prevent incompatibilities that could occur when mixing different formulation types together, such as emulsifiable concentrates and suspension concentrates.
Tank mixes can also include pesticide(s) dispersed or emulsified in a fertilizer solution. The adjuvants of the present invention function to facilitate the dispersion or emulsification of the pesticides(s) in the salt solutions by coupling the surfactants into the electrolyte solution.
The present invention is further illustrated by the following Examples.
Example 1 This example relates to a comparison between phosphated 2-propylheptanol +
5 EO and phosphated hexanol + 5 EO as hydrotropes for 2-propylheptanol + 5 EO.
Table 1 Formulation B
Compound Formulation A (Comparison) Phosphated 2-PH+5EO 3.5%
Phosphated 4.9%
hexanol+5EO
2-PH+5EO 5.0% 5.0%
Sodium metasilicate 4.0% 4.0%
Tetrapotassium 6.0% 6.0%
pyrophosphate Water 81.5% 80.1%
A smaller amount of phosphated 2-propylheptanol+5EO, as compared to phosphated hexanol+5EO, was required to obtain a clarity interval of 0-600C.
The formulations with phosphated 2-propylheptanol + 5 EO as a hydrotrope were also much more stable upon dilution.
Example 2 This example compares a number of phosphated ethoxylated alcohols with phosphated 2-propylheptanol + 5 EO as a hydrotrope for 2-propylheptanol + 5 EO.
Table 3 Compound 1 (Comparison) (Comparison) (Comparison) 2-PH+5EO 5.0% 5.0% 5.0% 5.0%
Phosphated 2- 3.5%
PH+5EO
Phosphated 3.0%
C9-CII-alcohol +5.5EO
Phosphated 3.4%
C9-C11-alcohol +4EO
Phosphated 2- 3.0%
ethyihexanol +4EO
Sodium 4.0 4.0 4.0 4.0 metasilicate Tetra- 6.0 6.0 6.0 6.0 potassium pyrophosphate Water 81.5 82.0 79.0 82.0 Table 4 Formu- Clarity Appearance Appearance Appearance Appearance Soil lation interval after dilution after dilution after dilution after dilution removal ( C) 1:5 after 1 1:20 after 1 1:5 after 1 1:20 after I at 1:20 day day week week dilution 1 0-70 Clear Clear Clear Hazy but 60.0 stable 2 0-53 Clear Clear Clear Clear 26.0 (COMP.) 3 0-60 Clear Clear Clear Clear 44.0 (Comp.) 4 0-50 Hazy Hazy Cloudy Hazy 54.0 (COMP.) The formulation according to the invention exhibited the best cleaning performance of all the investigated formulations, in combination with a good stability upon dilution.
Example 3 In this example the wetting ability of a composition according to the invention was measured by the modified Drave's test.
Table 5 Compound C
Phosphated 2-PH+5EO 6%
C9-Cll-alcohol+4EO 5.0%
Sodium nitrilotriacetate 10.0%
In the modified Drave's test, the sinking time in s is measured for a specified cotton yarn in approximately 0.1 % surfactant solution. The formulation in the Table 5 was diluted with distilled water to 0.1 % by weight with respect to the C9-C11-alcohol + 4 EO, and the modified Drave's test was performed on this solution. The result is displayed in the Table 6, below.
Table 6 Formulation Clarity interval pH Sinking time C (s) C 0-45 10.5 5 The formulation containing the phosphated 2-propylheptanol + 5 EO as a hydrotrope for the ethoxylate had a good wetting ability, whereas for the different components alone, the wetting time was >420 s. The C9-Cj -alcohol is not soluble in this alkaline medium without a hydrotrope, and the phosphated 2-propylheptanol + 5 EO has no good wetting ability on its own. When the hydrotrope is added, the nonionic surfactant is solubilised, and it is then able to exert its wetting ability.
Example 4 In the syntheses described below a 1,000 cm3 flange flask equipped with an anchor stirrer was used. The reactor was heated by an electrical heater equipped with a thermostat. A slight flow of nitrogen was applied during the 5 reaction. The polyphosphoric acid (PPA) used was Polyphosphoric acid 116, 84% equivalent in P205 (Albright & Wilson).
1) 2-propylheptanol + PPA
2-propylheptanol (222.47 g, 1.41 mole) was charged and heated to 45 C. PPA
10 (254.09 g) was added from a 60 ml syringe and the exothermic reaction was kept at 55-70 C while stirring at 240 r/min. PPA was added during a period of hour. The reaction was then left for 2 h at 60 C and with stirring at 300 r/min.
After the post-reaction water (5.0 g) was added to hydrolyse the remaining PPA, after which the acid was neutralised with KOH (274.4 g) dissolved in 555.0 g 15 water.
2) 2-propylheptanol + 3 EO +PPA
2-propylheptanol +3 EO (295.63 g, 1.02 mole) was charged and heated to
45 C. PPA (184.95 g) was added from a 60 ml syringe and the exothermic reaction was kept at 55-70 C while stirring at 240 r/min. PPA was added during 20 a period of 1 hour. The reaction was then left for 2 h at 60 C and with stirring at 300 r/min. After the post-reaction water (5.0 g) was added to hydrolyse the remaining PPA, after which the acid was neutralised with KOH (191 g) dissolved in 454 g water.
25 3) 2-propylheptanol + 5 EO + PPA
2-propylheptanol + 5 EO (307.71 g, 0.81 mole) was charged and heated to 45 C. PPA (148 g) was added from a 60 ml syringe and the exothermic reaction was kept at 55-70 C while stirring at 240 r/min. PPA was added during a period of 1 hour. The reaction was then left for 2 h at 60 C and with stirring at 300 30 r/min. After the post reaction water (5.0 g) was added to hydrolyse the remaining PPA, after which 374.02 g acid were neutralised with KOH (132.37 g) dissolved in 517 g water.
Example 5 Morwet D-425 is a condensed alkyl naphthalene sulfonate dispersant commercially available from Akzo Nobel Surface Chemistry LLC, Chicago, IL, that has been used as the main dispersant in various pesticide suspension concentrate, wettable powder and water dispersible granule formulations.
Frequently, a nonionic surfactant is used as a co surfactant to increase the wetting and stability of the formulations. Since the solubility of nonionic surfactants is decreased in the salt solution, flocculation will occur when pesticide formulation is mixed with fertilizer during application. This example is aimed to compare the performance of different co surfactant in Atrazine SC and to verify if the branched hydrophobe improves the compatibility in ammonium nitrate solution.
Materials Atrazine Tech.
Morwet D-425 (condensed alkyl naphthalene sulfonate, sodium salt) Ethylan 1005 phosphate ester (2-propyl heptanol + 5EO) Emphos PS - 131 (iso-tridecanol + 6EO, phosphate ester, acid form) Emphos PS-236 (linear C10/ 12 alcohol + 5EO, phosphate ester, acid form) Witconol SN-70 (linear C10/12 alcohol + 5EO) Witconol TD-60 (iso-tridecanol + 6EO) Ethylan 1005 (2-propyl heptanol + 5EO) Urea - ammonium nitrate The Atrazine suspensions were made by first dissolving the Morwet D-425 and wetting agent in the appropriate volume of water. Micronized Atrazine technical was then added to the solution and then dispersed using high shear. All of the suspensions tested were made to contain 480 grams per liter of active ingredient.
After preparing the Atrazine suspensions with different surfactant systems, the suspensions were diluted into UAN and evaluated based on the degree of flocculation as a function of time.
Formulations/Results/Observations Table 7. Atrazine formulations with different co surfactants Atrazine (g) D-425 (g) Co surfactant (g) Water (g) 1996-17-1 8.4 1.0 0.4 (1005 phosphate ester) 10.2 1996-17-2 8.4 1.0 0.4 (PS-131 10.2 1996-17-3 8.4 1.0 0.4 (TD-60) 10.2 1996-17-4 8.4 1.0 0.4 (Ethylan 1005) 10.2 1996-17-5 8.4 1.0 0.4 (PS-236) 10.2 1996-17-6 8.4 1.0 0.4 (SN-70) 10.2 1996-18-1 8.4 1.4 0.0 10.2 1996-18-2 8.4 1.0 0.0 10.6 1996-18-3 8.4 0.6 0.0 11.0 Next, 5 mL of each sample were poured in 95 mL of UAN solutions in 100 mL
tubes. The tubes were inverted 10 times and observed for flocculation. After sitting for 1, 2, 4, and 24 hours, the height of clear UAN solution from the bottom of tube was measured. The following results were found:
Table 8. Atrazine formulation performance in UAN solution 1 hr (cm) 2 hr (cm) 4 hr (cm) 24 hr (cm) 1996-17-1 14.0 17. 20.3 24.2 1996-17-2 22.5 23.3 24.4 25.7 1996-17-3 20.5 22.0 23.1 24.9 1996-17-4 19.0 20.0 21.1 22.7 1996-17-5 22.5 23.7 24.6 26.1 1996-17-6 20.0 21.0 22.1 24.4 1996-18-1 00 0.0 0.0 3.5 1996-18-2 0.0 0.0 0.4 3.2 1996-18-3 0.0 0.0 0.2 13.4 The invention is further illustrated by reference to FIG. 1 which is a plot illustrating atrazine formulation performance in UAN solution.
As seen above, all the co surfactants decreased the SC compatibility in UAN
solution because the salt precipitated the co surfactant from the system.
However, Ethylan 1005 phosphate ester (contained in sample 1996-17-1) did perform much better compared to other cosurfactants in the relatively short time period (up to 4 hr).
The difference in the results among formulations was significant enough to indicate that different hydrophobe lengths and branches can play an important role for compatibility issue.
Based on the data generated in this study, Ethylan 1005 phosphate ester showed the potential to improve the SC compatibility with UAN solution.
25 3) 2-propylheptanol + 5 EO + PPA
2-propylheptanol + 5 EO (307.71 g, 0.81 mole) was charged and heated to 45 C. PPA (148 g) was added from a 60 ml syringe and the exothermic reaction was kept at 55-70 C while stirring at 240 r/min. PPA was added during a period of 1 hour. The reaction was then left for 2 h at 60 C and with stirring at 300 30 r/min. After the post reaction water (5.0 g) was added to hydrolyse the remaining PPA, after which 374.02 g acid were neutralised with KOH (132.37 g) dissolved in 517 g water.
Example 5 Morwet D-425 is a condensed alkyl naphthalene sulfonate dispersant commercially available from Akzo Nobel Surface Chemistry LLC, Chicago, IL, that has been used as the main dispersant in various pesticide suspension concentrate, wettable powder and water dispersible granule formulations.
Frequently, a nonionic surfactant is used as a co surfactant to increase the wetting and stability of the formulations. Since the solubility of nonionic surfactants is decreased in the salt solution, flocculation will occur when pesticide formulation is mixed with fertilizer during application. This example is aimed to compare the performance of different co surfactant in Atrazine SC and to verify if the branched hydrophobe improves the compatibility in ammonium nitrate solution.
Materials Atrazine Tech.
Morwet D-425 (condensed alkyl naphthalene sulfonate, sodium salt) Ethylan 1005 phosphate ester (2-propyl heptanol + 5EO) Emphos PS - 131 (iso-tridecanol + 6EO, phosphate ester, acid form) Emphos PS-236 (linear C10/ 12 alcohol + 5EO, phosphate ester, acid form) Witconol SN-70 (linear C10/12 alcohol + 5EO) Witconol TD-60 (iso-tridecanol + 6EO) Ethylan 1005 (2-propyl heptanol + 5EO) Urea - ammonium nitrate The Atrazine suspensions were made by first dissolving the Morwet D-425 and wetting agent in the appropriate volume of water. Micronized Atrazine technical was then added to the solution and then dispersed using high shear. All of the suspensions tested were made to contain 480 grams per liter of active ingredient.
After preparing the Atrazine suspensions with different surfactant systems, the suspensions were diluted into UAN and evaluated based on the degree of flocculation as a function of time.
Formulations/Results/Observations Table 7. Atrazine formulations with different co surfactants Atrazine (g) D-425 (g) Co surfactant (g) Water (g) 1996-17-1 8.4 1.0 0.4 (1005 phosphate ester) 10.2 1996-17-2 8.4 1.0 0.4 (PS-131 10.2 1996-17-3 8.4 1.0 0.4 (TD-60) 10.2 1996-17-4 8.4 1.0 0.4 (Ethylan 1005) 10.2 1996-17-5 8.4 1.0 0.4 (PS-236) 10.2 1996-17-6 8.4 1.0 0.4 (SN-70) 10.2 1996-18-1 8.4 1.4 0.0 10.2 1996-18-2 8.4 1.0 0.0 10.6 1996-18-3 8.4 0.6 0.0 11.0 Next, 5 mL of each sample were poured in 95 mL of UAN solutions in 100 mL
tubes. The tubes were inverted 10 times and observed for flocculation. After sitting for 1, 2, 4, and 24 hours, the height of clear UAN solution from the bottom of tube was measured. The following results were found:
Table 8. Atrazine formulation performance in UAN solution 1 hr (cm) 2 hr (cm) 4 hr (cm) 24 hr (cm) 1996-17-1 14.0 17. 20.3 24.2 1996-17-2 22.5 23.3 24.4 25.7 1996-17-3 20.5 22.0 23.1 24.9 1996-17-4 19.0 20.0 21.1 22.7 1996-17-5 22.5 23.7 24.6 26.1 1996-17-6 20.0 21.0 22.1 24.4 1996-18-1 00 0.0 0.0 3.5 1996-18-2 0.0 0.0 0.4 3.2 1996-18-3 0.0 0.0 0.2 13.4 The invention is further illustrated by reference to FIG. 1 which is a plot illustrating atrazine formulation performance in UAN solution.
As seen above, all the co surfactants decreased the SC compatibility in UAN
solution because the salt precipitated the co surfactant from the system.
However, Ethylan 1005 phosphate ester (contained in sample 1996-17-1) did perform much better compared to other cosurfactants in the relatively short time period (up to 4 hr).
The difference in the results among formulations was significant enough to indicate that different hydrophobe lengths and branches can play an important role for compatibility issue.
Based on the data generated in this study, Ethylan 1005 phosphate ester showed the potential to improve the SC compatibility with UAN solution.
Claims (19)
1. An agricultural formulation comprising at least one agricultural active, and at least one agricultural adjuvant, wherein said adjuvant comprises at least one phosphated 2-propylheptanol, phosphated 2-propylheptanol alkoxylate, or mixtures thereof.
2. The formulation of claim 1, wherein the alkoxylate on average comprises 1 to 20 ethyleneoxy units and 0-3 propyleneoxy and/or butyleneoxy units.
3. The formulation of claim 1, wherein the phosphated 2-propylheptanol or the phosphated 2-propylheptanol alkoxylate has the formula:
where M is H, a monovalent metal ion or R1R2R3R4N+, where R1, R2, R3, and R4 are H, an alkyl group with 1-4 carbon atoms or -CH2CH2OH, and c is a number 0-20.
where M is H, a monovalent metal ion or R1R2R3R4N+, where R1, R2, R3, and R4 are H, an alkyl group with 1-4 carbon atoms or -CH2CH2OH, and c is a number 0-20.
4. The formulation of claim 3, wherein the adjuvant comprises a mixture containing two or more of:
- compounds of formula II, - compounds of the formula:
wherein n is 1-3 and M and c have the same meaning as in claim 3, - compounds of the formula:
wherein M and c have the same meaning as in claim 3, and - compounds of the formula:
wherein M and c have the same meaning as in claim 3, and where II is present in an amount of at least 60% by weight of the adjuvant mixture.
- compounds of formula II, - compounds of the formula:
wherein n is 1-3 and M and c have the same meaning as in claim 3, - compounds of the formula:
wherein M and c have the same meaning as in claim 3, and - compounds of the formula:
wherein M and c have the same meaning as in claim 3, and where II is present in an amount of at least 60% by weight of the adjuvant mixture.
5. The formulation of claim 1, wherein said phosphated 2-propylheptanol alkoxylate comprises 2 to 4 ethyleneoxy units.
6. The formulation of claim 5, wherein the phosphated alkoxylate comprises one or more products of the formulae:
wherein M is H, a monovalent metal ion or R1R2R3R4N+, where R1, R2, R3, and R4 are H, an alkyl group with 1-4 carbon atoms or -CH2CH2OH, and c is a number 2-4, wherein n is 1-3, M is H, a monovalent metal ion or R1R2R3R4N+, where R1, R2, R3, and R4 are H, an alkyl group with 1-4 carbon atoms or -CH2CH2OH, and c is a number 0-20, wherein M has the same meaning as above and c is a number 0-20, and wherein M has the same meaning as above and c is a number 0-20.
wherein M is H, a monovalent metal ion or R1R2R3R4N+, where R1, R2, R3, and R4 are H, an alkyl group with 1-4 carbon atoms or -CH2CH2OH, and c is a number 2-4, wherein n is 1-3, M is H, a monovalent metal ion or R1R2R3R4N+, where R1, R2, R3, and R4 are H, an alkyl group with 1-4 carbon atoms or -CH2CH2OH, and c is a number 0-20, wherein M has the same meaning as above and c is a number 0-20, and wherein M has the same meaning as above and c is a number 0-20.
7. The agricultural formulation of claim 1, which comprises 0.1-30% by weight of said adjuvant, and said adjuvant comprises phosphated 2-propylheptanol and/or a phosphated 2-propylheptanol alkoxylate, where the alkoxylate on average comprises 1 to 20 ethyleneoxy units and 0-3 propyleneoxy units.
8. The formulation of claim 7, wherein said adjuvant is a phosphated 2-propylheptanol alkoxylate comprising 2-4 ethyleneoxy units.
9. The formulation of claim 6, wherein in said one or more phosphated 2-propylheptanol alkoxylates having the formulae II, III, IV and/or V, the phosphated 2-propylheptanol alkoxylates having the formulae II is present in an amount of at least 80% by weight of the adjuvant mixture.
10. The formulation of any one of claims 1 to 9, wherein said adjuvant is a dispersant, emulsifier, hydrotrope, wetting agent, and/or compatability agent.
11. The formulation of any one of claims 1 to 10, wherein said at least one agricultural active is a herbicide, fungicide, insecticide, plant growth regulator, or mixtures thereof.
12. The use of at least one phosphated 2-propylheptanol, phosphated 2-propylheptanol alkoxylate, or mixtures thereof, as an adjuvant for an agricultural formulation.
13. The use of claim 12, wherein the alkoxylate on average comprises 1 to 20 ethyleneoxy units and 0-3 propyleneoxy and/or butyleneoxy units.
14. The use of claim 12 wherein the phosphated 2-propylheptanol or the phosphated 2-propylheptanol alkoxylate has the formula:
where M is H, a monovalent metal ion or R1R2R3R4N+, where R1, R2, R3, and R4 are H, an alkyl group with 1-4 carbon atoms or -CH2CH2OH, and c is a number 0-20.
where M is H, a monovalent metal ion or R1R2R3R4N+, where R1, R2, R3, and R4 are H, an alkyl group with 1-4 carbon atoms or -CH2CH2OH, and c is a number 0-20.
15. The use of claim 14, wherein the adjuvant comprises a mixture containing two or more of - compounds of formula II, - compounds of the formula:
wherein n is 1-3 and M and c have the same meaning as in claim 14, - compounds of the formula wherein M and c have the same meaning as in claim 14, and - compounds of the formula:
wherein M and c have the same meaning as in claim 14, and where II is present in an amount of at least 60% by weight of the adjuvant mixture.
wherein n is 1-3 and M and c have the same meaning as in claim 14, - compounds of the formula wherein M and c have the same meaning as in claim 14, and - compounds of the formula:
wherein M and c have the same meaning as in claim 14, and where II is present in an amount of at least 60% by weight of the adjuvant mixture.
16. The use of claim 12, wherein said phosphated 2-propylheptanolalkoxylate comprises 2 to 4 ethyleneoxy units.
17. The use of claim 16 wherein the phosphated alkoxylate comprises one or more products of the formulae:
wherein M is H, a monovalent metal ion or R1R2R3R4N+, where R1, R2, R3, and R4 are H, an alkyl group with 1-4 carbon atoms or -CH2CH2OH, and c is a number 2-4, wherein n is 1-3, M is H, a monovalent metal ion or R1R2R3R4N+, where R1, R2, R3, and R4 are H, an alkyl group with 1-4 carbon atoms or -CH2CH2OH, and c is a number 0-20, wherein M has the same meaning as above and c is a number 0-20, and wherein M has the same meaning as above and c is a number 0-20.
wherein M is H, a monovalent metal ion or R1R2R3R4N+, where R1, R2, R3, and R4 are H, an alkyl group with 1-4 carbon atoms or -CH2CH2OH, and c is a number 2-4, wherein n is 1-3, M is H, a monovalent metal ion or R1R2R3R4N+, where R1, R2, R3, and R4 are H, an alkyl group with 1-4 carbon atoms or -CH2CH2OH, and c is a number 0-20, wherein M has the same meaning as above and c is a number 0-20, and wherein M has the same meaning as above and c is a number 0-20.
18. The use of any one of claims 12 to 17, wherein said agricultural formulation is a herbicidal, fungicidal, insecticidal or plant growth regulator formulation, or a mixture thereof.
19. A method of treating plants which comprises contacting said plants with an agriculturally effective amount of the agricultural formulation of any one of claims 1 to 11.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04077043 | 2004-07-15 | ||
| EP04077043.0 | 2004-07-15 | ||
| US60816704P | 2004-09-08 | 2004-09-08 | |
| US60/608,167 | 2004-09-08 | ||
| PCT/US2005/024777 WO2006019772A1 (en) | 2004-07-15 | 2005-07-13 | Use of phosphated alcanols as dispersants, emulsifiers, hydrotropes, wetting agents and compatability agents in agricultural compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2573765A1 CA2573765A1 (en) | 2006-02-23 |
| CA2573765C true CA2573765C (en) | 2013-04-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CA2573765A Expired - Fee Related CA2573765C (en) | 2004-07-15 | 2005-07-13 | Use of phosphated alcanols as dispersants, emulsifiers, hydrotropes, wetting agents and compatibility agents in agricultural compositions |
Country Status (16)
| Country | Link |
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| US (1) | US8937033B2 (en) |
| EP (1) | EP1765072B1 (en) |
| JP (1) | JP4942651B2 (en) |
| AR (1) | AR049587A1 (en) |
| AT (1) | ATE468017T1 (en) |
| AU (1) | AU2005275217B2 (en) |
| BR (1) | BRPI0513288B1 (en) |
| CA (1) | CA2573765C (en) |
| DE (2) | DE602005011618D1 (en) |
| ES (1) | ES2345777T3 (en) |
| IL (1) | IL180667A (en) |
| NO (1) | NO20070746L (en) |
| NZ (1) | NZ552557A (en) |
| RU (1) | RU2370954C2 (en) |
| TW (1) | TWI378998B (en) |
| WO (1) | WO2006019772A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1765968B1 (en) * | 2004-07-15 | 2008-12-10 | Akzo Nobel N.V. | Phosphated alcanol, its use as a hydrotrope and cleaning composition containing the compound |
| JP5122841B2 (en) * | 2006-03-24 | 2013-01-16 | 石原産業株式会社 | Herbicidal composition |
| MX2011009317A (en) * | 2009-03-06 | 2012-02-23 | Syngenta Ltd | Compatibilized electrolyte formulations. |
| WO2011080207A1 (en) | 2009-12-30 | 2011-07-07 | Akzo Nobel Chemicals International B.V. | The use of a phosphated 2-propylheptanol ethoxylate as a bioefficacy enhancer, and a composition containing the phosphated 2-propylheptanol ethoxylate |
| CA2848515C (en) * | 2011-09-12 | 2017-07-18 | Rhodia Operations | Agricultural pesticide compositions |
| EP2839745A1 (en) * | 2013-08-21 | 2015-02-25 | Basf Se | Agrochemical formulations comprising a 2-ethyl-hexanol alkoxylate |
| CR20170330A (en) * | 2014-12-19 | 2018-01-10 | Azko Nobel Chemicals Int B V | UNIVERSAL DISPERSANT |
| US11632952B2 (en) | 2014-12-19 | 2023-04-25 | Nouryon Chemicals International B.V. | Universal dispersant |
| US11584857B2 (en) * | 2018-06-27 | 2023-02-21 | Dow Global Technologies Llc | Phosphate surfactant compositions |
| US20230286880A1 (en) | 2020-08-05 | 2023-09-14 | Syngenta Crop Protection Ag | Methods for improving the compatibility of crop protection formulations and tank mix applications with liquid fertilizers |
| IL299936A (en) | 2020-08-05 | 2023-03-01 | Syngenta Crop Protection Ag | Agricultural formulations having improved compatibility with liquid fertilizers |
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|---|---|---|---|---|
| US2871155A (en) * | 1957-03-20 | 1959-01-27 | Upjohn Co | Fungicidal composition comprising cycloheximide and solubilized lignin |
| NO121968C (en) * | 1966-06-23 | 1977-06-13 | Mo Och Domsjoe Ab | |
| GB1142425A (en) | 1967-05-04 | 1969-02-05 | Stauffer Chemical Co | Alkyl phosphate surfactants as primary emulsifiers in emulsion polymerization |
| GB2049427B (en) | 1979-03-28 | 1983-11-16 | Monsanto Co | Emusifiable concentrate formulations compatible with water and liquid fertilizers |
| DE3627023A1 (en) * | 1986-08-09 | 1988-02-11 | Hoechst Ag | PIGMENT DISPERSIONS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| US4975110A (en) * | 1989-10-13 | 1990-12-04 | Safer, Inc. | Fatty acid based herbicidal compositions |
| US5679351A (en) * | 1995-06-07 | 1997-10-21 | Thermo Trilogy Corporation | Clove oil as a plant fungicide |
| US6432884B1 (en) * | 1997-12-08 | 2002-08-13 | Cognis Corporation | Agricultural adjuvant |
| EP1765968B1 (en) | 2004-07-15 | 2008-12-10 | Akzo Nobel N.V. | Phosphated alcanol, its use as a hydrotrope and cleaning composition containing the compound |
-
2005
- 2005-07-08 DE DE602005011618T patent/DE602005011618D1/en active Active
- 2005-07-13 WO PCT/US2005/024777 patent/WO2006019772A1/en active Search and Examination
- 2005-07-13 DE DE602005021358T patent/DE602005021358D1/en active Active
- 2005-07-13 ES ES05770343T patent/ES2345777T3/en active Active
- 2005-07-13 BR BRPI0513288-6A patent/BRPI0513288B1/en not_active IP Right Cessation
- 2005-07-13 US US11/632,381 patent/US8937033B2/en not_active Expired - Fee Related
- 2005-07-13 AU AU2005275217A patent/AU2005275217B2/en not_active Ceased
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- 2005-07-13 JP JP2007521590A patent/JP4942651B2/en not_active Expired - Fee Related
- 2005-07-13 RU RU2007105583/15A patent/RU2370954C2/en not_active IP Right Cessation
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- 2005-07-13 CA CA2573765A patent/CA2573765C/en not_active Expired - Fee Related
- 2005-07-14 AR ARP050102916A patent/AR049587A1/en not_active Application Discontinuation
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- 2007-02-08 NO NO20070746A patent/NO20070746L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| AU2005275217A2 (en) | 2006-02-23 |
| DE602005011618D1 (en) | 2009-01-22 |
| RU2370954C2 (en) | 2009-10-27 |
| AU2005275217A1 (en) | 2006-02-23 |
| DE602005021358D1 (en) | 2010-07-01 |
| AU2005275217B2 (en) | 2011-10-27 |
| EP1765072A1 (en) | 2007-03-28 |
| BRPI0513288B1 (en) | 2014-07-15 |
| JP4942651B2 (en) | 2012-05-30 |
| ATE468017T1 (en) | 2010-06-15 |
| AR049587A1 (en) | 2006-08-16 |
| WO2006019772A1 (en) | 2006-02-23 |
| CA2573765A1 (en) | 2006-02-23 |
| IL180667A (en) | 2015-08-31 |
| BRPI0513288A (en) | 2008-05-06 |
| NO20070746L (en) | 2007-04-13 |
| JP2008506693A (en) | 2008-03-06 |
| US20080051289A1 (en) | 2008-02-28 |
| EP1765072B1 (en) | 2010-05-19 |
| IL180667A0 (en) | 2007-06-03 |
| WO2006019772A8 (en) | 2006-05-18 |
| US8937033B2 (en) | 2015-01-20 |
| ES2345777T3 (en) | 2010-10-01 |
| RU2007105583A (en) | 2008-09-10 |
| NZ552557A (en) | 2010-10-29 |
| TWI378998B (en) | 2012-12-11 |
| TW200619378A (en) | 2006-06-16 |
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